Linear copolyester containing phosphorous, procedure for its preparation and its use as a flame-retardant additive

ABSTRACT

A linear copolyester is prepared by polycondensation of an aromatic bicarboxylic acid with an alkylene glycol and with a carboxyphosphinic acid or anhydride which produces monomeric units having the formula: ##STR1## wherein R 1  is an alkylene or phenyl radical and R 2  is an alkyl or phenyl radical. 
     This copolyester can be used as a flame-retardant additive for organic polymers.

This is a division of application U.S. Ser. No. 08/247,525, filed on May23, 1994, now U.S. Pat. No. 5,550,207, which is a file wrappercontinuation of U.S. Ser. No. 07/992,591, now abandoned and filed onDec. 18, 1992 for LINEAR COPOLYESTER CONTAINING PHOSPHORUS, PROCEDUREFOR ITS PREPARATION AND ITS USE AS A FLAME-RESISTANT ADDITIVE.

The present invention relates to linear polyesters containing structuralunits based on phosphorous, the procedure for their preparation andtheir use as flame-retardant agents.

In the field of organic polymers there is a demand for flame-resistantproducts, especially in certain areas of application such as the textileindustry.

Various flame-retardant additives, generally halogenated organiccompounds or compounds containing phosphorous, are used and are appliedby surface treatment of the product, for example in the finishing stageof a textile.

However, the use of these flame-retardant additives is not generallycompletely satisfactory, mainly because of their incompatibility withthe organic polymers to which they are added, the release of theadditive from the polymer and the high quantities of additive requiredto provide the necessary flame-retardant characteristics.

In accordance with another technique, the flame-retardantcharacteristics are obtained by introducing monomeric units containingphosphorous into the polymeric chain.

For example, flame-retardant linear polyesters are known in the art,obtained by polycondensing, in the presence of suitable catalysts,terephthalic acid, or its methyl diester, with an alkylene glycol, suchas ethylene glycol, and with at least one monomeric unit containingphosphorous.

For example U.S. Pat. Nos. 3,941,752 and 4,033,936 describeflame-retardant linear polyesters obtained by the polycondensation of abicarboxylic acid, an alkylene glycol and a monomer deriving from aphosphinic carboxy acid, one of its esters or its cyclic anhydride(2,5-dioxo-1,2-oxaphospholane), the latter in quantities ranging from 3to 20 moles % with respect to the total quantity of acid components.

The use of these monomers containing phosphorous in the reaction for thepreparation of the flame-retardant polymer may however causedisadvantages, due, for example, to the necessity of modifying theproduction plant of the polymer.

It has now been found that linear copolyesters containing highquantities of phosphorous in the macromolecule can be prepared and canbe used as flame-retardant additives in the stabilization of a widerange of organic polymers, without having any of the disadvantages ofthe known art.

The present invention consequently relates to a linear copolyester, aflame-retardant additive for organic polymers, composed of the productof the polycondensation of an aromatic bicarboxylic acid with analkylene glycol containing from 2 to 6 carbon atoms and with a monomerwhich produces in the chain of said copolyester units having theformula: ##STR2## wherein R₁ is a linear alkylene radical, branched orcyclic containing from 1 to 6 carbon atoms, or a substituted ornon-substituted phenyl radical, R₂ is an alkyl radical containing from 1to 6 carbon atoms, or a substituted or non-substituted phenyl radical,said copolyester having a phosphorous content of at least 2.5% byweight, and preferably in the range of 3-6%.

Suitable bicarboxylic aromatic acids are, for example, terephthalic acidand isophthalic acid. Among these terephthalic acid is preferred.

Among the alkylene glycols containing from 2 to 6 carbon atoms, ethyleneglycol, 1,4-butandiol, neopentylglycol and 1,4-cyclohexandiol arepreferred. Particularly preferred is ethylene glycol.

In the units having formula (I), R₁ is preferably an alkylene radicalcontaining 2 carbon atoms, whereas R₂ is preferably a methyl or phenyl.

Compounds which produce units having formula (I) in the copolyesterchain are carboxy-phosphinic acids having the formula: ##STR3## theiresters with an alcohol containing from 1 to 4 carbon atoms or with adiol containing from 2 to 4 carbon atoms, in the latter case possibly inthe form of oligomers containing up to 5 monomeric units, or it is alsopossible to use the corresponding cyclic anhydrides having the formula:##STR4## with R¹ and R² which, in both formulae (II) and (III), have themeaning defined above.

The linear copolyesters of the present invention are prepared accordingto a method, which is a further aspect of the present invention, andwhich consists in the polycondensation reaction of the respectivecomonomers, and i.e. of bicarboxylic aromatic acid, of alkylene glycoland of the carboxyphosphinic monomer which produce the units havingformula (I).

The above copolyesters may also be prepared by a precondensation of thecarboxyphosphinic compound with alkylene glycol, and subsequenttreatment of these glycol esters with a prepolymer of bicarboxylicaromatic acid and alkylene glycol.

The linear copolyesters of the present invention are used asflame-retardant additives, suitable for providing flame-resistantcharacteristics to a wide range of organic polymers, such as linearpolyesters with an aliphatic and/or aromatic structure, polyolefins,polyamides, polycarbonates, polyphenylenoxides, polystyrenes, di- andter-styrene polymers such as SAN and ABS, elastomeric copolymers such asEPR, EPDM, EVA.

In particular, the flame-retardant copolyester of the present inventionis mixed and homogenized during the processing of the organic polymer inthe molten state, which can then be transformed into end-products suchas fibres, films, moulded items, etc.

The polymeric additives of the present invention are extremelycompatible with the above organic polymers, forming real polymericbinders with these, and are also able to remain for long time within thepolymeric material in which they are incorporated.

The quantity of copolyester of the present invention which is necessaryfor giving flame-retardant characteristics should be sufficient toensure a phosphorous content (evaluated as an element) in the organicpolymer ranging from 0.3 to 3% by weight, and preferably from 0.6 to1.5% by weight.

The following examples provide a better illustration of the presentinvention but do not limit it in any way.

EXAMPLE 1

15 g of 1,2-oxaphospholane-5-one-2-methyl-2-oxide and 45 g of ethyleneglycol are charged into a three-necked 250 cc flask equipped with amechanical stirrer, nitrogen inlet and condenser.

The temperature is brought, under a N₂ atmosphere, to 120°-130° C., atwhich temperature the anhydride passes into solution. These conditionsare maintained for 90 minutes, after which the excess glycol isdistilled at reduced pressure, thus dehydrating the reaction mass at thesame time.

The latter is then reacted with 60 g of a polyethyleneterephthalateprepolymer (PET) having a viscosity index V.I.=0.23 dl/g and containing205 ppm of Sb (as Sb₂ O₃). The reactor is evacuated and cleaned threetimes with N₂, and the system is then put under forced vacuum for 20minutes.

The N₂ atmosphere is subsequently restored and the temperature broughtto 250° C. by means of a heating fluid. After the homogeneous fusion ofthe mass, the temperature is brought to 275° C. and the pressure to 400mm Hg over a period of 30 minutes. After an hour at constant temperatureand continually increasing vacuum, a forced vacuum is applied and thesystem is spontaneously brought to 0.2 mm Hg.

The reaction mass becomes more and more viscous and after a further 90minutes the condensation operation is concluded and 73.8 g of acopolyester are recovered at room temperature with the followingelemental analysis: C=57.05%; H=5.10%; P=4.29%. The characteristics ofthe above polyester are shown in Table I.

The value of the melting DH, expressed as J/g, and the peak meltingpoint, expressed in degrees centigrade, are determined by differentialscan calorimetry (DSC), operating with a METTLER DSC 30 apparatus in anitrogen atmosphere, with a gradient of 10° C./minute, within atemperature range of 35° to 300° C.

EXAMPLE 2

Using the same procedure described in example 1, 30 g of1,2-oxaphospholane-5-one-2-methyl-2-oxide and 90 g of ethylene glycolare reacted at 120°-130° C. for 60 minutes.

40 cc of excess glycol are distilled and 0.5 g of tin-dibutyl-dilaurateare added to the anhydried reaction mass. The mixture is condensed at atemperature ranging from 175°-196° C. for 8 hours with a vacuum from 300to 0.05 mm of Hg.

32.4 g of a distillate of ethylene glycol are obtained, whereas theresidual product is characterized and is found to be anoligo-methyl-phosphin-β-propionate of ethylene glycol having 16.3% ofphosphorous and a condensation degree of 3.36.

36.2 g of the above oligomer are reacted with 160 g of a PET prepolymerhaving a V.I.=0.40 dl/g and containing 245 ppm of Sb (as Sb₂ O₃) at aconstant temperature of 275° C. for two hours with a vacuum decreasingfrom 4 to 0.05 mm of Hg.

About 160 g of a copolyester are obtained with the following elementalanalysis: C=57.09%; H=4.60%; P=3.09%.

EXAMPLE 3

Using the same procedure described in example 1, 23.35 g ofphenyl-phosphin-β-propionic acid, 70 g of ethylene glycol and 60 g of aPET prepolymer with a V.I.=0.23 del/g containing 205 ppm of Sb (as Sb₂O₃), are made to react.

81.7 g of a copolyester are obtained with the following elementalanalysis: C=59.51%; H=4.88%; P=4.03%.

EXAMPLE 4

Using the same procedure described in example 1, 32.42 g of1,2-oxaphospholan-5-one-2-phenyl-2-oxide and 97 g of ethylene glycoland, after esterification and anhydrification, 95.85 g of a PETprepolymer with a V.I.=0.23 del/g containing 205 ppm of Sb (as Sb₂ O₃),are charged.

123 g of a copolyester are obtained with the following elementalanalysis: C=59.6%; H=4.77%; P=3.76%.

EXAMPLE 5

Using the same procedure described in example 1, 43.89 g of1,2-oxaphospholan-5-one-2-phenyl-2-oxide, 97 g of ethylene glycol and64.50 g of a PET prepolymer with a V.I.=0.23 del/g containing 205 ppm ofSb (as Sb₂ O₃), are charged.

111.2 g of a copolyester are obtained with the following elementalanalysis: C=59.26%; H=4.80%; P=5.45%.

EXAMPLE 6

Using the same procedure described in example 1, 120 g of1,2-oxaphospholan-5-one-2-phenyl-2-oxide, and 250 g of ethylene glycolare made to react at 120°-130° C. for 90 minutes.

106 g of glycol are distilled at reduced pressure and 145 g ofoligo-phenyl-β-propionate of ethylene glycol are recovered as a residuehaving 12.51% of phosphorous and a condensation degree of 5.63.

72 g of the above oligomer are reacted with 123 g of a PET prepolymerhaving a V.I.=0.40 dl/g and containing 245 ppm of Sb (as Sb₂ O₃) at atemperature of 270°-275° C. for 70 minutes under a vacuum of 3 to 0.05mm of Hg.

About 143 g of a copolyester are obtained with the following elementalanalysis: C=59.26%; H=4.80%; P=4.57%.

EXAMPLE 7

14 parts of pellets of copolyester of example 1 are mixed with 86 partsof pellets of a polyethyleneterephthalate having a V.I.=0.65 dl/g andacidity of 20 meq/kg.

This blend is dried at 130° C. for 4 hours and spun directly on anautomatic semi-industrial machine equipped with an extruder having 38 mmscrews and 4 spinnerets of 45 mm in diameter.

A 50 dtex fibre is obtained with 10 circular floss operating with arecovery rate of 1200 m/minute. The phosphorous content is 0.6%.

These fibres, wound onto a spool after ensambling, are used to obtaintubular "socks" having a diameter of 10 cm which, when subjected to theLimited Oxygen Index (L.O.I.) flammability test, give a value of 31%.The L.O.I. for an identical product obtained without the addition of PETis 22%.

EXAMPLE 8

Using the same procedure described in example 7 a PET containing 18.6%of the copolyester of example 4 is spun.

The textile samples obtained show a L.O.I. of 33.5%.

EXAMPLE 9

A pre-dried blend composed of chips of commercial (Pibiter N 100)polybutyleneterephthalate (PBT) and of the copolyester of example 5,with a weight ratio of 78:22, is extruded in a Werner Pfleiderer ZSK 25twin-screw extruder.

Test samples having a thickness of 1/16 inch are injection moulded withthe extruded polymer for the UL94 vertical test.

The PBT with this additive is classified VO.

                  TABLE 1                                                         ______________________________________                                                ΔH melting                                                                        Peak melting                                                                             T.sub.g   Equivalent                             Additive                                                                              (J/g)     point (°C.)                                                                       (°C.)                                                                       P %  weight                                 ______________________________________                                        Example 1                                                                             20.14     177.8      44.0 4.29 23,300                                 Example 2                                                                             28.34     249.8      47.0 3.09 8,245                                  Example 3                                                                             --        --         50.0 4.03 9,900                                  Example 4                                                                             --        --         46.0 3.76 13,230                                 Example 5                                                                             --        --         44.6 5.45 4,908                                  Example 6                                                                             26.64     242.9      --   4.57 2,830                                  ______________________________________                                    

We claim:
 1. An organic polymer selected from the group consisting oflinear polyesters having an aliphatic and/or aromatic structure,polyolefins, polyamides, polycarbonates, polyphenylene oxides, styrenepolymers, ethylene-propylene rubbers, ethylene-propylene-diene monomers,and ethylene vinyl acetate, which organic polymers are flame-stabilizedby the addition of a linear copolyester composed of the polycondensationproduct of a dicarboxylic aromatic acid with a C₂ -C₆ alkylene glycoland with a monomer which, in the chain of the copolyester, producesunits having the formula: ##STR5## where R₁ represents a linear,branched or cyclic alkylene radical and R₂ represents a C₁ -C₆ alkylgroup or a phenyl radical; the copolyester having a phosphorous contentequal to at least 2.5% by weight.
 2. The organic polymer of claim 1,wherein the copolyester has a phosphorus content of 4.03 to 6% byweight.
 3. The organic polymer of claim 1, wherein the dicarboxylicaromatic acid is terephthalic acid or isophthalic acid.
 4. The organicpolymer of claim 3, wherein the dicarboxylic aromatic acid isterephthalic acid.
 5. The organic polymer of claim 3, wherein thealkylene glycol is a C₂ -C₆ alkylene glycol.
 6. The organic polymer ofclaim 3, wherein the alkylene glycol is ethylene glycol, 1,4-butanediol,or neopentyl glycol.
 7. The organic polymer of claim 6, wherein thealkylene glycol is ethylene gylcol.
 8. The organic polymer of claim 1,wherein R₂ is a methyl group.
 9. The organic polymer of claim 1, whereinR₂ is the phenyl group.
 10. The organic polymer of claim 3, wherein thephosphorous-containing monomer is selected from the group consisting of(a) a carboxyphosphinic acid having the formula ##STR6## (b) an esterthereof with a C₁ -C₄ alcohol or a C₂ -C₄ diol, (c) an oligomer of theester containing up to 5 monomer units, and a (d) a cyclic anhydridethereof having the formula ##STR7## where R₁ is a C₁ -C₆ linear,branched, or cyclic alkylene group and R₂ is a C₁ -C₆ alkyl group or aphenyl group.
 11. The organic polymer of claim 3, wherein thedicarboxylic aromatic acid is terephthalic acid; wherein the alkyleneglycol is ethylene glycol; and wherein, in the monomer, R₁ is a C₂alkylene group and R₂ is a methyl group.
 12. The organic polymer ofclaim 1, wherein R₂ is the methyl group.
 13. The organic polymer ofclaim 3, wherein the dicarboxylic aromatic acid is terephthalic acid;wherein the alkylene glycol is ethylene glycol; wherein thephosphorous-containing monomer is selected from (a) carboxyphosphinicacid having the formula ##STR8## (b) an ester thereof with a C₁ -C₄alcohol or a C₂ -C₄ diol, (c) an oligomer of the ester containing up to5 monomer units, and (d) a cyclic anhydride thereof having the formula##STR9## where R₁ is a C₁ -C₆ linear, branched, or cyclic alkylene groupand R₂ is a C₁ -C₆ alkyl group or a phenyl group.
 14. The organicpolymer of claim 1, wherein the polymer is polyethylene terephthalate.15. The organic polymer of claim 2, wherein the polymer is polyethyleneterephthalate.
 16. The organic polymer of claim 13, wherein the polymeris polyethylene terephthalate.
 17. The organic polymer of claim 1,wherein the polymer is polybutylene terephthalate.
 18. The organicpolymer of claim 2, wherein the polymer is polybutylene terephthalate.19. The organic polymer of claim 13, wherein the polymer is polybutyleneterephthalate.